Modified alkoxylated polyol compounds

ABSTRACT

A modified polyol compound having alkoxylation and having at least one anionic capping unit, uses of the modified polyol compound having alkoxylation and having at least one anionic capping unit and cleaning compositions comprising the same.

CROSS REFERENCE TO RELATED APPLICATION

This application is a Divisional Application of U.S. application Ser.No. 11/015,574, filed Dec. 17, 2004, which claims the benefit under 35U.S.C. § 119(e) of U.S. provisional application No. 60/531,385, filedDec. 19, 2003.

FIELD OF THE INVENTION

This invention relates to modified alkoxylated polyol compounds, methodsof making modified alkoxylated polyol compounds, and cleaningcompositions comprising the same.

BACKGROUND OF THE INVENTION

Polyol compounds such as sugars like sucrose or maltitose are known as asustainable and readily available raw material. Ethoxyates of maltitolis known, e.g., CAS 503446-80-8. This material has been widely disclosedas a surfactant for cosmetic and other personal care applications suchas that discussed in JP 2003-096182. Other known ethoxylated polyolsinclude: ethoxylated manitol (CAS 53047-01-2), ethoxylated inostol (CAS503446-79-5), ethoxylated sorbitol (CAS 53694-15-8). JP 10-081744discusses the production of polyetherpolyols by adding alkylene oxidesto saccharide in the presence of amine catalysts. However, as “catalyst”implies, the amine catalysts do not become incorporated into thepolyetherpolyol structure.

Also known are a series of amine terminated ethoxylates known in thetrade as JEFFAMINES® sold by Huntsman. These are mainly derived frompolyethylene glycol and mixtures of polyethylene glycol andpolypropylene glycol where the glycols are aminated directly withammonia and a catalyst. These are called JEFFAMINE D® and JEFFAMINE ED®series. The most complex mixture of the JEFFAMINES® series is the Tseries. The JEFFAMINES® are based on either trimethylolpropane orglycerine and thus have three ammonia terminated ethoxy/propoxy branchesradiating from the glycerin or trimethylolpropane core.

Amination of polyols with ammonia and other amines is furtherexemplified in U.S. Pat. No. 5,371,119, but uses modification of thepolyol specifically via epichlorohydrin to form a polyol bis-halohydrinfollowed by reaction with ammonia or an amine to form repeating networksof amino polyols. This results in formation of a complex polymerizedmixture containing multiple polyols linked randomly via the reactivehalo hydrin. This complex mixture is not believed to be of value toformulators of cleaning compositions for the purpose of providingcleaning benefits and is targeted towards forming emulsifiers.

Simple amination of polyols are described in WO 01/98388 A1 discussingsimple aminated polyols, further reacted with aldehydes, in particularformaldehyde, to make complex polymeric networks. Included in thesecomplex structures is the ability to have sulfide, carboxylate, alkylesters, alkyl sulphonates, and alkyl phosphates as a functional unit ofthe complex structure. However, the resulting complex polymeric networksis not believed to be of value to formulators of cleaning compositionsfor the purpose of providing cleaning benefits. Additionally, it has notbeen taught to manipulate these materials in a controlled and specificmanner. Selective modification of sugar derived polyols to providemodified polyols where the star like structure is tuned to meet theneeds of detergent formulators is highly desirable.

There also exists a need for materials that are relatively easy tomanufacture from sustainable and readily available raw materials, whichmay be broadly tuned to address specific performance requirements.

Stressed conditions also give the additional problem of having anionicsurfactants such as linear alkylbenzene sulfonates or alkyl sulfatesform larger order aggregates. The aggregation of the anionic surfactantreduces the amount of the anionic surfactant available to clean.

There exists a need for materials that are relatively easy tomanufacture from sustainable and readily available raw materials, whichmay be tuned in a controlled and specific manner to address specificformulability and performance requirements. A multifunctional materialthat provides cleaning and gives increased surfactant availability bypreventing formation of larger ordered aggregates of anionic surfactantwith free hardness during use is desired.

Specific performance requirements include providing cleaning ofhydrophobic stains (grease, oil) to hydrophilic stains (clay) associatedwith outdoor soils. Other performance requirements include used inpersonal care compositions, such as contact lens solution, uses inadhesives, vulcanization of rubbers, use in polyurethane processes, useas dye additives, use as a dispersant in agricultural applications, useas dispersants for inks, asphalt dispersants, surfactant dissolutionaides, in use surfactant solubilizers in presence of calcium andmagnesium among other performance requirements.

Formulability of some of the current commercial polymers, which providecleaning of outdoor soils, into granular and liquid laundry detergents,hard surface cleaners, dish cleaning compositions, personal carecompositions as well as oil drilling compositions continues to challengedetergent formulators.

SUMMARY OF THE INVENTION

The present invention relates to compounds, processes, cleaningcompositions, and methods of using said compounds and compositionscharacterized by comprising a polyol compound, the polyol compoundcomprising at least three hydroxy moieties, at least one of the hydroxymoieties further comprising a alkoxy moiety, the alkoxy moiety isselected from the group consisting of ethoxy, propoxy, butoxy andmixtures thereof; further wherein at least one of the hydroxy moietiesfurther comprise an anionic capping unit.

The present invention further relates compounds, processes, cleaningcompositions, and methods of using said compounds and compositionscharacterized by comprising a polyol compound, the polyol compoundcomprising at least three hydroxy moieties, at least one of the hydroxymoieties further comprising a alkoxy moiety, the alkoxy moiety isselected from the group consisting of ethoxy, propoxy, butoxy andmixtures thereof; further wherein at least one of the hydroxy moietiesis replaced by and thus further comprises an anionic capping unit and atleast one of the hydroxy moieties is substituted by an amine cappingunit.

The present invention further relates compounds, processes, cleaningcompositions, and methods of using said compounds and compositionscharacterized by comprising a polyol compound, the polyol compoundcomprising at least three hydroxy moieties, at least one of the hydroxymoieties further comprising a alkoxy moiety, the alkoxy moiety isselected from the group consisting of ethoxy, propoxy, butoxy andmixtures thereof; further wherein at least one of the hydroxy moietiesis replaced by and thus further comprises an anionic capping unit and atleast one of the hydroxy moieties is substituted by a quaternary aminecapping unit.

The present invention further relates compounds, processes, cleaningcompositions, and methods of using said compounds and compositionscharacterized by comprising a polyol compound, the polyol compoundcomprising at least three hydroxy moieties, at least one of the hydroxymoieties further comprising a alkoxy moiety, the alkoxy moiety isselected from the group consisting of ethoxy, propoxy, butoxy andmixtures thereof; further wherein at least one of the hydroxy moietiesis replaced by and thus further comprises an anionic capping unit, atleast one of the hydroxy moieties is substituted by an amine cappingunit and at least one of the hydroxy moieties is substituted by aquaternary amine capping unit.

DETAILED DESCRIPTION OF THE INVENTION

There exists a need for materials that are relatively easy tomanufacture from sustainable and readily available raw materials, whichmay be broadly tuned to address specific formulability and performancerequirements.

Polyol compounds such as sugar based materials andpolyethylene/polypropylene glycol materials are sustainable and readilyavailable raw materials that lend themselves to be broadly tuned toaddress specific formulability and performance requirements. As usedherein “tune” means having the ability to manipulate the chemicalstructure of the polyol compounds to achieve distinguishing chemicalfunctionality. For example, an alkoxylated polyol compound modified bycomprising an anionic capping unit is a tuned structure giving desiredcharacteristics for specific formulability and performance requirements.Another example, an alkoxylated polyol compound modified by comprisingan anionic capping unit and amine capping unit is a tuned structuregiving desired characteristics. Another example is when an alkoxylatedpolyol compound is modified by comprising an anionic capping unit and aquaternary amine capping unit, is a tuned structure giving desiredcharacteristics. Finally another example may contain both elements ofthe two examples, thus containing an anionic capping unit and an amineand quaternary amine capping unit.

The polyol compounds useful in the present invention comprises at leastthree hydroxy moieties, preferably more than three hydroxy moieties.Most preferably six or more hydroxy moieties. At least one of thehydroxy moieties further comprising a alkoxy moiety, the alkoxy moietyis selected from the group consisting of ethoxy (EO), propoxy (PO),butoxy (BO) and mixtures thereof preferably ethoxy and propoxy moieties,more preferably ethoxy moieties. The average degree of alkoxylation isfrom about 1 to about 100, preferably from about 4 to about 60, morepreferably from about 10 to about 40. Alkoxylation is preferably blockalkoxylation.

The polyol compounds useful in the present invention further have atleast one of the alkoxy moieties comprising at least one anionic cappingunit. Further modifications or tuning of the compound may occur, but oneanionic capping unit must be present in the compound of the presentinvention. One embodiment comprises more than one hydroxy moiety furthercomprising an alkoxy moiety having an anionic capping unit. For exampleformula (I):

wherein x of formula (I) is from about 1 to about 100, or such as fromabout 10 to about 40.

Suitable anionic capping unit include sulfate, sulfosuccinate,succinate, maleate, phosphate, phthalate, sulfocarboxylate,sulfodicarboxylate, propanesultone, 1,2-disulfopropanol,sulfopropylamine, sulphonate, monocarboxylate, methylene carboxylate,ethylene carboxylate, carbonates, mellitic, pyromellitic, sulfophenol,sulfocatechol, disulfocatechol, tartrate, citrate, acrylate,methacrylate, poly acrylate, poly acrylate-maleate copolymer, andmixtures thereof. Preferably the anionic capping units are sulfate,sulfosuccinate, succinate, maleate, sulfonate, methylene carboxylate andethylene carboxylate.

Suitable polyol compounds for starting materials for use in the presentinvention include maltitol, sucrose, xylitol, glycerol, pentaerythitol,glucose, maltose, matotriose, maltodextrin, maltopentose, maltohexose,isomaltulose, sorbitol, poly vinyl alcohol, partially hydrolyzedpolyvinylacetate, xylan reduced maltotriose, reduced maltodextrins,polyethylene glycol, polypropylene glycol, polyglycerol, diglycerolether and mixtures thereof. Good examples include the polyol compoundbeing selected as sorbitol, maltitol, sucrose, xylan, polyethyleneglycol, polypropylene glycol and mixtures thereof. Another group for thepolyol compound is sorbitol, maltitol, sucrose, xylan, and mixturesthereof.

Tuning of the polyol compounds can be derived from one or moremodifications, dependant upon the desired formulability and performancerequirements. Tuning requires anionic modifications and can includeincorporating a cationic or zwitterionic charge modifications to thepolyol compounds.

In one embodiment of the present invention, at least one hydroxy moietycomprises an alkoxy moiety, wherein the alkoxy moiety further comprisesat least one anionic capping unit.

In another embodiment of the present invention, at least one hydroxymoiety comprises an alkoxy moiety, wherein the alkoxy moiety furthercomprises more than one anionic capping unit, wherein at least oneanionic capping unit, but less than all anionic capping units, is thenselectively substituted by a amine capping unit. The amine capping unitis selected from a primary amine containing capping unit, a secondaryamine containing capping unit, a tertiary amine containing capping unit,and mixtures thereof.

Suitable primary amines for the primary amine containing capping unitinclude monoamines, diamine, triamine, polyamines, and mixtures thereof.Suitable secondary amines for the secondary amine containing cappingunit include monoamines, diamine, triamine, polyamines, and mixturesthereof. Suitable tertiary amines for the tertiary amine containingcapping unit include monoamines, diamine, triamine, polyamines, andmixtures thereof.

Suitable monoamines, diamines, triamines or polyamines for use in thepresent invention include ammonia, methyl amine, dimethylamine, ethylenediamine, dimethylaminopropylamine, bis dimethylaminopropylamine (bisDMAPA), hexemethylene diamine, benzylamine, isoquinoline, ethylamine,diethylamine, dodecylamine, tallow triethylenediamine, mono substitutedmonoamine, monosubstituted diamine, monosubstituted polyamine,disubstituted monoamine, disubstiuted diamine, disubstituted polyamine,trisubstituted triamine, tri-substituted polyamine, multisubstitutedpolyamine comprising more than three substitutions provided at least onenitrogen contains a hydrogen, and mixtures thereof.

In another embodiment of the present invention, at least one ofnitrogens in the amine capping unit is quaternized. As used herein“quaternized” means that the amine capping unit is given a positivecharge through quaternization or protonization of the amine cappingunit. For example, bis-DMAPA contains three nitrogens, only one of thenitrogens need be quaternized. However, it is preferred to have allnitrogens quaternized on any given amine capping unit.

The tuning or modification may be combined depending upon the desiredformulability and performance requirements. Non-limiting examples ofmodified polyol compounds of the present invention include:

formula (II)wherein x of formula (I) is from about 1 to about 100; andsuch as from about 10 to about 40.

Process of Making

The present invention also relates to a process for making the compoundof the present invention. The process for making the compound of thepresent invention comprises the optional step of alkoxylating a polyolcompound comprising at least three hydroxy moieties such that theaverage degree of alkoxylation of at least one hydroxy moiety is betweenabout 1 and about 100; and such as from about 4 to about 60; furthersuch as from about 10 to about 40; to form an alkoxylated polyolcomprising at least one alkoxy moiety. Alternatively, an alkoxylatedpolyol, such as CAS 52625-13-5, a propoxylated sorbitol or sorbitolpolyoxy ethylene ether available from Lipo Chemicals Inc., may be usedas the starting material of the present invention. If the average degreeof alkoxylation is not a desired level, an alkoxylation step may be usedto achieve the desired degree of alkoxylation from about 1 to about 100,and such as from about 4 to about 60; further such as from about 10 toabout 40. Next, the process comprises the step of reacting at least onealkoxy moiety of the compound with an anionic capping unit to form ananionic alkoxylated polyol, although more anionic capping units may beselected.

In one embodiment the process comprises another step of substituting atleast one anionic capping unit of the anionic alkoxylated polyol with anamine capping unit to form an anionic aminated alkoxylated polyol. Inthis process only certain anionic capping units may be substituted suchas sulfate, phosphate and carbonate. The process may further comprisethe step of quaternizing at least one of the nitrogens in the aminecapping of the anionic aminated alkoxylated polyol to form azwitterionic alkoxylated polyol. Quaternization can be performed on anyof the anionic aminated alkoxylated polyols. In one embodiment, theprocess comprises the step of alkoxylating some or most of the hydroxymoieties of the polyol such that the degree of alkoxylation is fromabout 1 to about 100; and such as from about 4 to about 60, further suchas from about 10 to about 40; to form an alkoxylated polyol. The processfurther comprises the step of reacting the alkoxy moiety of thealkoxylated polyol with at least one anionic capping unit containing asleast one of the following anionic groups; sulfate, phosphate andcarbonate; to form an anionic alkoxylated polyol. The process maypartially or completely react the alkoxy moiety of the alkoxylatedpolyol with an anionic capping unit. It is also understood that anioniccapping units other than sulfate, phosphate or carbonate may also bepresent in the anionic alkoxylated polyol. Preferably all alkoxymoieties comprise an anionic capping unit.

Optionally, the process comprises the step of substituting the anioniccapping unit with an amine capping unit selected from sulfate, phosphateand carbonate and mixtures thereof, to form an aminated anionicalkoxylated polyol (scheme I below). The substitution of the anioniccapping units present with an amine capping unit may be partial orcomplete. Preferably the subsitution of the anionic capping unit withthe amine capping unit is partial forming an anionic aminatedalkoxylated polyol.

Optionally, the process also comprises the process of providing anaminated alkoxylated polyol by direct amination of the alkoxylatedpolyol using catalytic amination (scheme II below)

Optionally, the process may further comprise the step of quaternizing atleast one of the nitrogens of the amine capping unit of the anionicaminated alkoxylated polyol forming a zwitterionic alkoxylated polyol.The quaternization of the amine capping unit of the anionic aminatedalkoxylated polyol may be partial or complete. In one embodiment, thequaternization is partial. In another embodiment, the quaternization iscomplete. The quaternization of the nitrogens of the amine capping unitmay be partial or complete, preferably complete. A nonlimiting synthesisscheme is exemplified in Synthesis Scheme I and Synthesis Scheme IIbelow:

The process may comprise optionally Step 1, Step 2, and optionally, Step3 and 4. The step to providing the anionic aminated alkoxylated polyolvia a neucleophilic substitution of sulfate moieties by an amine cappingunit should be noted. This is a nonlimiting example as phosphate orcarbonate groups may also be used for substitution by an amine cappingunit.

Scheme II is distinguished from Scheme I in two areas; (1) directsubstitution of the terminal hydroxy moieties is accomplished bycatalytic oxidation/reduction using metal catalysts and hydrogen; (2)sulfation is carried out after amination and quaternization bytransulfation as disclosed in U.S. Pat. No. 6,452,035. A zwitterionicalkoxylated polyol of the same composition may be prepared by eitherScheme I or Scheme II above. One of skill in the art will recognizedthat other amine capping units may be used, including but not limited toammonia or dimethylaminopropylamine.

A specific description of the process of the present invention isdescribed in more detail below.

Ethoxylation of Polyol

Ethoxylation of the polyol, such as sorbitol, may be completed by anyknown technique, such as that described in EP 174436 A1 Propoxylationand butoxylation may also be completed by known techniques.

Add sorbitol (17.5 g, 0.0962 mol) to an autoclave, purge the autoclavewith nitrogen, heat sorbitol to 110-120° C.; autoclave stirred and applyvacuum to about 20 mmHg.

Vacuum is continuously applied while the autoclave is cooled to about110-120° C. while introducing 6.2 g of a 25% sodium methoxide inmethanol solution (0.0288 moles, to achieve a 5% catalyst loading basedupon hydroxy moieties). The methanol from the methoxide solution isremoved from the autoclave under vacuum. A device is used to monitor thepower consumed by the agitator. The agitator power is monitored alongwith the temperature and pressure. Agitator power and temperature valuesgradually increase as methanol is removed from the autoclave and theviscosity of the mixture increases and stabilizes in about 1.5 hoursindicating that most of the methanol has been removed. The mixture isfurther heated and agitated under vacuum for an additional 30 minutes.

Vacuum is removed and the autoclave is cooled to or kept at 110° C.while it is being charged with nitrogen to 1725 kPa (250 psia) and thenvented to ambient pressure. The autoclave is charged to 1380 kPa (200psia) with nitrogen. Ethylene oxide is added to the autoclaveincrementally while closely monitoring the autoclave pressure,temperature, and ethylene oxide flow rate while maintaining thetemperature between 110 and 120° C. and limiting any temperatureincreases due to reaction exotherm. After the addition of 483 g ofethylene oxide (10.97 mol, resulting in a total of 19 moles of ethyleneoxide per mol of OH), the temperature is increased to 120° C. and themixture stirred for an additional 2 hours.

The reaction mixture is then collected into a 22 L three neck roundbottomed flask purged with nitrogen. The strong alkali catalyst isneutralized by slow addition of 2.8 g methanesulfonic acid (0.00288moles) with heating (110° C.) and mechanical stirring. The reactionmixture is then purged of residual ethylene oxide and deodorized bysparging an inert gas (argon or nitrogen) into the mixture through a gasdispersion frit while agitating and heating the mixture to 120° C. for 1hour. The final reaction product, approximately 500 g, is cooledslightly, and poured into a glass container purged with nitrogen forstorage.

Alternatively, polyol may be purchased with a degree of alkoxylationthat is at or below that desired, such as CAS 52625-13-5, a propoxylatedsorbitol or sorbitol polyoxy ethylene ether available from LipoChemicals Inc. Wherein the desired degree of alkoxylation is achieved bythe processes known and/or described above.

Sulfation of Sorbitol EO₁₁₄ (Average of 19 EO Moieties Per HydroxyMoiety)

Weigh into a 500 ml Erlenmeyer flask Sorbitol E₁₁₄ (299.7 g, 0.058 mol)and methylene chloride (300 g) (“the solution”)_. Equip the flask with amagnetic stirring bar and stir until complete dissolution. Place theflask in an ice bath until the solution reaches about 10° C. Stirvigorous while slowing pouring chlorosulfonic acid (48.3 g, 0.415 mol)over the period of about 5 minutes to form a reaction solution. Stir thereaction solution in the ice bath for 1.5 hours.

Place a solution of sodium methoxide (197 g of 25% in methanol) in 50 gof methylene chloride in a IL Erlenmeyer flask (“base solution”) andchill in an ice bath until the temperature of the solution reaches about10° C. Stir the base solution vigorous using a magnetic stirring bar.Slowly pour the reaction solution into the base solution over a periodof about 3 minutes. A mild exotherm should be observed. The resultingsolution becomes milky as salts form. After addition is complete,measure the pH to be about 12. Add to this resulting solution about 100ml of distilled water, and transfer the resulting emulsion to a 1 Lround bottom flask and use a rotary evaporator at 50° C. to strip, inportions, to obtain a clear solution. Transfer the clear solution to aKulgelrohr apparatus. At 60° C. and 133 Pa (1 mm Hg) strip the solutionto yield 366 g of off-white waxy solid, 90% active (10% salts).

Carbon NMR spectrum (500 MHz; pulse sequence: s2pul, solvent D₂O; relax.delay 0.300 sec, pulse 45.0; acq. time 1.090 sec) shows an absence ofalcohol groups at about 60 ppm and the emergence of a new peak at about67 ppm consistent with formation of the end group sulfate. Proton NMRspectrum (500 MHz or 300 MHz; pulse sequence: s2pul, solvent D₂O; relax.delay 1.000 sec, pulse 45.0; acq. time 2.345 sec) shows a new peak atabout 4 ppm which was integrated against the ethoxy group protons atabout 3.5 ppm and is consistent with the molecule having 6 end groupsulfates.

EXAMPLE 2 Amination of Sorbitol EO₁₁₄ Hexasulfate Of Example 1

Weigh into a 200 ml glass liner sorbitol EO₁₁₄ hexasulfate (61.3 g of90% active, 0.0095 mol) and 3-(dimethylamino)propylamine (“DMAPA” 18.5g, 0.181 mol). Heat the liner in a rocking autoclave at 152 kPa (150psig) under nitrogen until the temperature reaches 165° C. and hold at165° C. for 2 hours. Cool to room temperature (20-25° C.). Take thematerial up in 150 ml of methylene chloride and centrifuge to separatethe salts. Transfer the supernatant to a 500 ml round bottom flask andstrip the supernatant on a rotary evaporator at 50° C. until most (lessthan 5 mL) of the solvent is removed. Heat on a Kugelrohr apparatus at120° C. and 133 Pa (1 mm Hg) for 30 minutes to remove excess amine toafford 47.8 g of brown hard solid. Proton NMR (500 MHz or 300 MHz; pulsesequence: s2pul, solvent D₂O; relax. delay 0.300 sec, pulse 45.0; acq.time 3.744 sec) indicated about 3 sulfates and about 2 DMAPA permolecule.

EXAMPLE 3 Quaternization of Amine Containing Sulfate Of Example 2

Dissolve an aminated Sorbitol EO₁₁₄ in 100 g of methylene chloride in a500 ml round bottom flask equipped with a magnestic stirring bar andchill in an ice bath until the temperature reaches 10° C. Adjust thesolution to a pH 12 with sodium methoxide (25% solution in methanol).Add to the solution methyl iodide (15.0 g, 0.106 mol). Stopper the flaskand stir the solution overnight (about 14 hours). Strip the solution ona Kugelrohr apparatus at 50° C. and 133 Pa (1 mm Hg) to afford 66 g oftacky brown solid. Proton NMR (500 MHz or 300 MHz; pulse sequence:s2pul, solvent D₂0; relax. delay 1.000 sec, pulse 45.0; acq. time 2.345sec) indicated that all nitrogens in the amine capping unit were fullyquaternized.

Cleaning Compositions

The present invention further relates to a cleaning compositioncomprising the modified alkoxylated polyol compound of the presentinvention. The cleaning compositions can be in any conventional form,namely, in the form of a liquid, powder, granules, agglomerate, paste,tablet, pouches, bar, gel, types delivered in dual-compartmentcontainers, spray or foam detergents, premoistened wipes (i.e., thecleaning composition in combination with a nonwoven material such asthat discussed in U.S. Pat. No. 6,121,165, Mackey, et al.), dry wipes(i.e., the cleaning composition in combination with a nonwovenmaterials, such as that discussed in U.S. Pat. No. 5,980,931, Fowler, etal.) activated with water by a consumer, and other homogeneous ormultiphase consumer cleaning product forms.

In addition to cleaning compositions, the compounds of the presentinvention may be also suitable for use or incorporation into industrialcleaners (i.e. floor cleaners). Often these cleaning compositions willadditionally comprise surfactants and other cleaning adjunctingredients, discussed in more detail below. In one embodiment, thecleaning composition of the present invention is a liquid or solidlaundry detergent composition.

In another embodiment, the cleaning composition of the present inventionis a hard surface cleaning composition, preferably wherein the hardsurface cleaning composition impregnates a nonwoven substrate. As usedherein “impregnate” means that the hard surface cleaning composition isplaced in contact with a nonwoven substrate such that at least a portionof the nonwoven substrate is penetrated by the hard surface cleaningcomposition, preferably the hard surface cleaning composition saturatesthe nonwoven substrate.

In another embodiment the cleaning composition is a liquid dish cleaningcomposition, such as liquid hand dishwashing compositions, solidautomatic dishwashing cleaning compositions, liquid automaticdishwashing cleaning compositions, and tab/unit does forms of automaticdishwashing cleaning compositions.

The cleaning composition may also be utilized in car care compositions,for cleaning various surfaces such as hard wood, tile, ceramic, plastic,leather, metal, glass. This cleaning composition could be also designedto be used in a personal care composition such as shampoo composition,body wash, liquid or solid soap and other cleaning composition in whichsurfactant comes into contact with free hardness and in all compositionsthat require hardness tolerant surfactant system, such as oil drillingcompositions.

Modified Alkoxylated Polyol Compounds

The cleaning composition of the present invention may comprise fromabout 0.005% to about 30%, and such as from about 0.01% to about 10%,further such as from about 0.05% to about 5% by weight of the cleaningcomposition of a modified polyol compound as described herein.

Surfactants—The cleaning composition of the present invention maycomprise a surfactant or surfactant system comprising surfactantsselected from nonionic, anionic, cationic, ampholytic, zwitterionic,semi-polar nonionic surfactants; and other adjuncts such as alkylalcohols, or mixtures thereof. The cleaning composition of the presentinvention further comprises from about from about 0.01% to about 90%,and such as from about 0.01% to about 80%, further such as from about0.05% to about 50%, more further such as from about 0.05% to about 40%by weight of the cleaning composition of a surfactant system having oneor more surfactants.

Anionic Surfactants

Nonlimiting examples of anionic surfactants useful herein include:C₈-C₁₈ alkyl benzene sulfonates (LAS); C₁₀-C₂₀ primary, branched-chainand random alkyl sulfates (AS); C₁₀-C₁₈ secondary (2,3) alkyl sulfates;C₁₀-C₁₈ alkyl alkoxy sulfates (AE,S) wherein x is from 1-30; C₁₀-C₁₈alkyl alkoxy carboxylates comprising 1-5 ethoxy units; mid-chainbranched alkyl sulfates as discussed in U.S. Pat. No. 6,020,303 and U.S.Pat. No. 6,060,443; mid-chain branched alkyl alkoxy sulfates asdiscussed in U.S. Pat. No. 6,008,181 and U.S. Pat. No. 6,020,303;modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO99/05242 and WO 99/05244; methyl ester sulfonate (MES); and alpha-olefinsulfonate (AOS).

Nonionic Surfactants

Non-limiting examples of nonionic surfactants include: C₁₂-C₁₈ alkylethoxylates, such as, NEODOL® nonionic surfactants from Shell; C₆-C₁₂alkyl phenol alkoxylates wherein the alkoxylate units are a mixture ofethyleneoxy and propyleneoxy units; C₁₂-C₁₈ alcohol and C₆-C₁₂ alkylphenol condensates with ethylene oxide/propylene oxide block alkylpolyamine ethoxylates such as PLURONIC® from BASF; C₁₄-C₂₂ mid-chainbranched alcohols, BA, as discussed in U.S. Pat. No. 6,150,322; C₁₄-C₂₂mid-chain branched alkyl alkoxylates, BAEX, wherein x 1-30, as discussedin U.S. Pat. No. 6,153,577, U.S. Pat. No. 6,020,303 and U.S. Pat. No.6,093,856; Alkylpolysaccharides as discussed in U.S. Pat. No. 4,565,647Llenado, issued Jan. 26, 1986; specifically alkylpolyglycosides asdiscussed in U.S. Pat. No. 4,483,780 and U.S. Pat. No. 4,483,779;Polyhydroxy fatty acid amides (GS-base) as discussed in U.S. Pat. No.5,332,528; and ether capped poly(oxyalkylated) alcohol surfactants asdiscussed in U.S. Pat. No. 6,482,994 and WO 01/42408.

Cationic Surfactants

Non-limiting examples of anionic surfactants include: the quaternaryammonium surfactants, which can have up to 26 carbon atoms include:alkoxylate quaternary ammonium (AQA) surfactants as discussed in U.S.Pat. No. 6,136,769; dimethyl hydroxyethyl quaternary ammonium asdiscussed in Pat. No. 6,004,922; polyamine cationic surfactants asdiscussed in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO98/35006; cationic ester surfactants as discussed in U.S. Pat. Nos.4,228,042, 4,239,660 4,260,529 and U.S. Pat. No. 6,022,844; and aminosurfactants as discussed in U.S. Pat. No. 6,221,825 and WO 00/47708,specifically amido propyldimethyl amine (APA).

Zwitterionic Surfactants

Non-limiting examples of zwitterionic surfactants include: derivativesof secondary and tertiary amines, derivatives of heterocyclic secondaryand tertiary amines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678to Laughlin et al., issued Dec. 30, 1975 at column 19, line 38 throughcolumn 22, line 48, for examples of zwitterionic surfactants; betaine,including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine,C₈ to C₁₈ (C₁₂ to C₁₈) amine oxides and sulfo and hydroxy betaines, suchas N-alkyl-N,N-dimethylammino-1-propane sulfonate where the alkyl groupcan be C₈ to C₁₈, C₁₀ to C₁₄.

Ampholytic Surfactants

Non-limiting examples of ampholytic surfactants include: aliphaticderivatives of secondary or tertiary amines, or aliphatic derivatives ofheterocyclic secondary and tertiary amines in which the aliphaticradical can be straight- or branched-chain. One of the aliphaticsubstituents contains at least about 8 carbon atoms, typically fromabout 8 to about 18 carbon atoms, and at least one contains an anionicwater-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S.Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column19, lines 18-35, for examples of ampholytic surfactants.

Semi-Polar Nonionic Surfactants

Non-limiting examples of semi-polar nonionic surfactants include:water-soluble amine oxides containing one alkyl moiety of from about 10to about 18 carbon atoms and 2 moieties selected from the groupconsisting of alkyl groups and hydroxyalkyl groups containing from about1 to about 3 carbon atoms; water-soluble phosphine oxides containing onealkyl moiety of from about 10 to about 18 carbon atoms and 2 moietiesselected from the group consisting of alkyl groups and hydroxyalkylgroups containing from about 1 to about 3 carbon atoms; andwater-soluble sulfoxides containing one alkyl moiety of from about 10 toabout 18 carbon atoms and a moiety selected from the group consisting ofalkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.See WO 01/32816, U.S. Pat. No. 4,681,704, and U.S. Pat. No. 4,133,779.

Gemini Surfactants

Gemini Surfactants are compounds having at least two hydrophobic groupsand at least two hydrophilic groups per molecule have been introduced.These have become known as “gemini surfactants” in the literature, e.g.,Chemtech, March 1993, pp 30-33, and J. American Chemical Soc., 115,10083-10090 (1993) and the references cited therein.

Cleaning Adjunct Materials

In general, a cleaning adjunct is any material required to transform acleaning composition containing only the minimum essential ingredientsinto a cleaning composition useful for laundry, hard surface, personalcare, consumer, commercial and/or industrial cleaning purposes. Incertain embodiments, cleaning adjuncts are easily recognizable to thoseof skill in the art as being absolutely characteristic of cleaningproducts, especially of cleaning products intended for direct use by aconsumer in a domestic environment.

The precise nature of these additional components, and levels ofincorporation thereof, will depend on the physical form of the cleaningcomposition and the nature of the cleaning operation for which it is tobe used.

The cleaning adjunct ingredients if used with bleach should have goodstability therewith. Certain embodiments of cleaning compositions hereinshould be boron-free and/or phosphate-free as required by legislation.Levels of cleaning adjuncts are from about 0.00001% to about 99.9%, andsuch as from about 0.0001% to about 50% by weight of the cleaningcompositions. Use levels of the overall cleaning compositions can varywidely depending on the intended application, ranging for example from afew ppm in solution to so-called “direct application” of the neatcleaning composition to the surface to be cleaned.

Quite typically, cleaning compositions herein such as laundrydetergents, laundry detergent additives, hard surface cleaners,synthetic and soap-based laundry bars, fabric softeners and fabrictreatment liquids, solids and treatment articles of all kinds willrequire several adjuncts, though certain simply formulated products,such as bleach additives, may require only, for example, an oxygenbleaching agent and a surfactant as described herein. A comprehensivelist of suitable laundry or cleaning adjunct materials can be found inWO 99/05242.

Common cleaning adjuncts include builders, enzymes, polymers notdiscussed above, bleaches, bleach activators, catalytic materials andthe like excluding any materials already defined hereinabove. Othercleaning adjuncts herein can include suds boosters, suds suppressors(antifoams) and the like, diverse active ingredients or specializedmaterials such as dispersant polymers (e.g., from BASF Corp. or Rohm &Haas) other than those described above, color speckles, silvercare,anti-tarnish and/or anti-corrosion agents, dyes, fillers, germicides,alkalinity sources, hydrotropes, anti-oxidants, enzyme stabilizingagents, pro-perfumes, perfumes, solubilizing agents, carriers,processing aids, pigments, and, for liquid formulations, solvents,chelating agents, dye transfer inhibiting agents, dispersants,brighteners, suds suppressors, dyes, structure elasticizing agents,fabric softeners, anti-abrasion agents, hydrotropes, processing aids,and other fabric care agents, surface and skin care agents. Suitableexamples of such other cleaning adjuncts and levels of use are found inU.S. Pat. Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1.

Method of Use

The present invention includes a method for cleaning a surface orfabric. Such method includes the steps of contacting a modifiedalkoxylated polyol compound of the present invention or an embodiment ofthe cleaning composition comprising the modified alkoxylated polyolcompound of the present invention, in neat form or diluted in a washliquor, with at least a portion of a surface or fabric then optionallyrinsing such surface or fabric. Preferably the surface or fabric issubjected to a washing step prior to the aforementioned optional rinsingstep. For purposes of the present invention, washing includes but is notlimited to, scrubbing, and mechanical agitation.

As will be appreciated by one skilled in the art, the cleaningcompositions of the present invention are ideally suited for use in homecare (hard surface cleaning compositions), personal care and/or laundryapplications. Accordingly, the present invention includes a method forcleaning a surface and/or laundering a fabric. The method comprises thesteps of contacting a surface and/or fabric to be cleaned/laundered withthe modified alkoxylated polyol compound or a cleaning compositioncomprising the modified alkoxylated polyol compound. The surface maycomprise most any hard surface being found in a typical home such ashard wood, tile, ceramic, plastic, leather, metal, glass, or may consistof a cleaning surfaces in a personal care product such as hair and skin.The surface may also include dishes, glasses, and other cookingsurfaces. The fabric may comprise most any fabric capable of beinglaundered in normal consumer use conditions.

The cleaning composition solution pH is chosen to be the mostcomplimentary to a surface to be cleaned spanning broad range of pH,from about 5 to about 11. For personal care such as skin and haircleaning pH of such composition preferably has a pH from about 5 toabout 8 for laundry cleaning compositions pH of from about 8 to about10. The compositions are preferably employed at concentrations of fromabout 200 ppm to about 10,000 ppm in solution. The water temperaturespreferably range from about 5° C. to about 100° C.

For use in laundry cleaning compositions, the compositions arepreferably employed at concentrations from about 200 ppm to about 10000ppm in solution (or wash liquor). The water temperatures preferablyrange from about 5° C. to about 60° C. The water to fabric ratio ispreferably from about 1:1 to about 20:1.

The present invention included a method for cleaning a surface orfabric. Such method includes the step of contacting a nonwoven substrateimpregnated with an embodiment of the cleaning composition of thepresent invention, and contacting the nonwoven substrate with at least aportion of a surface and/or fabric. The method may further comprise awashing step. For purposes of the present invention, washing includesbut is not limited to, scrubbing, and mechanical agitation. The methodmay further comprise a rinsing step.

As used herein “nonwoven substrate” can comprise any conventionallyfashioned nonwoven sheet or web having suitable basis weight, caliper(thickness), absorbency and strength characteristics. Examples ofsuitable commercially available nonwoven substrates include thosemarketed under the tradename SONTARA® by DuPont and POLYWEB® by JamesRiver Corp.

As will be appreciated by one skilled in the art, the cleaningcompositions of the present invention are ideally suited for use in hardsurface applications. Accordingly, the present invention includes amethod for cleaning hard surfaces. The method comprises the steps ofcontacting a hard surface to be cleaned with a hard surface solution ornonwoven substrate impregnated with an embodiment of the cleaningcomposition of the present invention. The method of use comprises thesteps of contacting the cleaning composition with at least a portion ofthe nonwoven substrate, then contacting a hard surface by the hand of auser or by the use of an implement to which the nonwoven substrateattaches.

As will be appreciated by one skilled in the art, the cleaningcompositions of the present invention are ideally suited for use inliquid dish cleaning compositions. The method for using a liquid dishcomposition of the present invention comprises the steps of contactingsoiled dishes with an effective amount, typically from about 0.5 ml. toabout 20 ml. (per 25 dishes being treated) of the liquid dish cleaningcomposition of the present invention diluted in water. Suitable examplesmay be seen below in Table 5.

Generally, from about 0.01 ml. to about 150 ml. of a liquid dishcleaning composition of the invention is combined with from about 2000ml. to about 20000 ml of water in a sink having a volumetric capacity inthe range of from about 1000 ml. to about 20000 ml. The soiled dishesare immersed in the sink containing the diluted compositions thenobtained, where contacting the soiled surface of the dish with a cloth,sponge, or similar article cleans them. The cloth, sponge, or similararticle may be immersed in the detergent composition and water mixtureprior to being contacted with the dish surface, and is typicallycontacted with the dish surface for a period of time ranged from about 1to about 10 seconds. The contacting of cloth, sponge, or similar articleto the dish surface is preferably accompanied by a concurrent scrubbingof the dish surface.

Another method of use will comprise immersing the soiled dishes into awater bath without any liquid dish cleaning composition. A device forabsorbing liquid dish cleaning composition, such as a sponge, is placeddirectly into a separate quantity of undiluted liquid dish cleaningcomposition for a period of time typically ranging from about 1 to about5 seconds. The absorbing device, and consequently the undiluted liquiddish cleaning composition, is then contacted individually to the surfaceof each of the soiled dishes to remove said soiling. The absorbingdevice is typically contacted with each dish surface for a period oftime range from about 1 to about 10 seconds. The contacting of theabsorbing device to the dish surface is preferably accompanied byconcurrent scrubbing.

As will be appreciated by one skilled in the art, the cleaningcompositions of the present invention are also suited for use inpersonal cleaning care applications. Accordingly, the present inventionincludes a method for cleaning skin or hair. The method comprises thesteps of contacting a skin / hair to be cleaned with a cleaning solutionor nonwoven substrate impregnated with an embodiment of the cleaningcompositions discussed herein. The method of use of the nonwovensubstrate when contacting skin and hair may be by the hand of a user orby the use of an implement to which the nonwoven substrate attaches.

Other Compositions

Other compositions that comprise the compound of the present inventionmay be used in personal care compositions, such as contact lenssolution, used as adhesives, in the vulcanization of rubbers, used inpolyurethane manufacturing processes, used in dye compositions, used asan ink composition, used as a dispersant in agricultural applications,such as a dispersant in an antifungal composition, among othercompositions.

Formulations TABLE 1 Liquid Laundry Cleaning Compositions A Ingredients[% by wt.] Linear 10-15 alkylbenzenesulfonate C₁₂₋₁₅ alcoholethoxy_((1.1-2.5)) 1-5 sulfate C₁₂₋₁₃ alcohol 1-5 ethoxylate₍₇₋₉₎cocodimethyl amine 0.1-1   oxide fatty acid 1-5 citric acid 1-5 Polymerc¹ 0.5-3   hydroxylated castor  5-20 oil (structurant) Water, perfumes,ad 100 dyes, and other trace components

polymer according to any one of Examples 1-3 and formula I-IV of thepresent application. TABLE 2 Low Sudsing Granular Laundry CleaningCompositions B C D wt % wt % wt % C₁₁₋₁₂ Linear alkyl benzene 7 5.1 10.2sulphonate C_(12-18(tallow)) alkyl sulfate 1 1 1 C₁₄₋₁₅ alkyl ethoxylate3.2 3.2 3.2 (EO = 7) APA¹ 0.94 0.68 1.36 silicate builder² 4.05 — —Zeolite A³ 16.65 — — Carbonate⁴ 14.04 — — Citric Acid (Anhydrous) 2.932.93 2.93 acrylic acid/maleic acid 0.97 0.97 0.97 copolymer⁵ Polymer⁶1-5 1-5 1-5 Percarbonate 12.8 16.18 13.25 tetraacetylethylenediamine3.64 5.92 3.95 1-hydroxyethyidene-1,1- 0.18 0.18 0.18 diphosphonic acidS,S-(ethylenediamine N,N′- 0.2 0.2 0.2 disuccinic acid) MgSO₄ 0.42 0.420.42 ENZYMES⁷ (% particle) 1.26 1.26 1.26 MINORS (perfume, dyes, Ad AdAd suds stabilizers) 100 100 100¹C₈₋₁₀ amido propyl dimethyl amine²Amorphous Sodium Silicate (SiO₂:Na₂O; 2.0 ratio)³Hydrated Sodium Aluminosilicate of formula Na₁₂(A10₂SiO₂)₁₂•27H₂Ohaving a primary particle size in the range from 0.1 to 10 micrometers⁴Anhydrous sodium carbonate with a particle size between 200 μm and 900μm⁵4:1 acrylic acid/maleic acid, average molecular weigh about 70,000 or6:4 acrylic acid/maleic acid, average molecular weight about 10,000)⁶polymer according to any one of Examples 1-3 or formula I-IV of thepresent invention⁷one or more enzymes such as: Protease - Proteolytic enzyme, having 3.3%by weight of active enzyme, sold by NOVO Industries A/S under thetradename SAVINASE ®; Proteolytic enzyme, having 4% by weight of activeenzyme, as described in WO 95/10591, sold by Genencor Int. Inc.Alcalase - Proteolytic enzyme, having 5.3% by weight of active enzyme,sold by NOVO Industries A/S# Cellulase - Cellulytic enzyme, having 0.23% by weight of activeenzyme, sold by NOVO Industries A/S under the tradename CAREZYME ®.Amylase - Amylolytic enzyme, having 1.6% by weight of active enzyme,sold by NOVO Industries A/S under the tradename TERMAMYL 120T ®;Amylolytic enzyme, as disclosed in PCT/US9703635. # Lipase - Lipolyticenzyme, having 2.0% by weight of active enzyme, sold by NOVO IndustriesA/S under the tradename LIPOLASE ®; Lipolytic enzyme, having 2.0% byweight of active enzyme, sold by NOVO Industries A/S under the tradenameLIPOLASE ULTRA ®. Endolase - Endoglucanase enzyme, having 1.5% by weightof active enzyme, sold by NOVO Industries A/S.

TABLE 3 Granular Laundry Cleaning Compositions E F G H wt % wt % wt % wt% C₁₀₋₁₂ linear 13.4-15.0 15.2-17.2 12.7 12.7 alkyl sulphonate C₁₂₋₁₄alkyl 2.8 2.8 3.0 3.0 ethoxylate (EO = 9) Builder¹ 18 — — — Sequestrant²— 17 — — enzyme 0.35 0.40 — — Polymer³ 1-2 1-2 1 1 Carboxy 0.2 0.2 0.5 —Methyl Cellulose suds 0.01 0.01 — — suppressor⁴ Polyacrylate⁵ 0.80 0.80.5 buffer 4.0 2.0 6.0 6.0 Carbonate 11.0 15.0 8.0 8.0 brightener 0.080.08 0.03 0.03 Sodium 34.83 32.33 65.09 65.09 Sulfate Water and Ad Ad AdAd minors 100 100 100 100¹sodium tripolyphosphate²Zeolite A: Hydrated Sodium Aluminosilicate of formulaNa₁₂(A10₂SiO₂)₁₂•27H₂O having a primary particle size in the range from0.1 to 10 micrometers³An modified alkoxylated polyol compound according to Examples 1-3 andformula I-IV of the present application⁴suds suppressor⁵Mw = 4500

TABLE 4 Hard Surface Cleaning Compositions floor cleaning floor cleaningwipe solution I solution J wt % wt % C₁₁ alcohol ethoxylate 0.03 0.03(EO = 5) Sodium C₈ Sulfonate 0.01 0.01 Propylene Glycol n-Butyl 2 2Ether 2-Phenoxyethanol 0.05 0.05 Ethanol 3 Polymer¹ 0.015 0.0152-Dimethylamino-2- 0.01 0.01 methyl-2-propanol (DMAMP) perfume 0.01-0.060.01-0.06 Suds suppressor² 0.003 0.003 2-methyl-4-isothaizolin- 0.015 —3one + chloro derivative Water and minors Ad 100 Ad 100¹polymer according to Examples 1-3 and formula I-IVof the presentapplication.²such as Dow Corning AF Emulsion or polydimethyl siloxane

TABLE 5 Liquid Dishwashing Cleaning Composition K L M C₁₂₋₁₃ alcoholethoxylate sulfate EO = 0.6 26 23 24 Amine Oxide 5.8 5.8 5.8 C₈₋₁₂alcohol ethoxylate EO = 8 2 2 2 Ethanol 2 2 2 Sodium cumene sulfonate1.80 1.80 1.80 NaCl 1.4 1.4 1.4 MgCl₂ 0.2 0.2 0.2 Suds Booster¹ 0.2 0.20.2 Polymer² 0.8 0.8 0.8 Water & other trace components (i.e., dye, ad100 ad 100 ad 100 perfume, diamine, etc.)¹as described in U.S. Pat. No. 6,645,925 B1²a polymer according to Examples 1-3 and formula I-IV of the presentinvention.

The dimensions and values disclosed herein aer not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”.

All documents cited in the Detailed Description of the Invention are,are, in relevant part, incorporated herein by reference; the citation ofany document is not to be construed as an admission that it is prior artwith respect to the present invention.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1. A process for making a compound characterized by comprising a polyolcompound, the polyol compound comprising at least three hydroxymoieties, at least one of the hydroxy moieties further comprising aalkoxy moiety, the alkoxy moiety is selected from the group consistingof ethoxy, propoxy, butoxy and mixtures thereof; further wherein atleast one of the, hydroxy moieties further comprise an anionic cappingunit; wherein the process comprises the steps of (a) alkoxylating apolyol compound comprising at least three hydroxy moieties such that theaverage degree of alkoxylation of at least one hydroxy moiety is betweenabout 1 and about 100, to form an alkoxylated polyol comprising at leastone alkoxy moiety; (b) reacting the alkoxy moiety of the alkoxylatedpolyol with at least one anionic capping unit to form an anionicalkoxylated polyol.
 2. The process of claim 1 further comprising thestep of substituting the anionic capping unit consisting of sulfate,phospate or carbonate or mixtures thereof, with an amine capping unit toform an aminated anionic alkoxylated polyol which wherein other anioniccapping units.
 3. The process of claim 2 further comprising the step ofquaternizing at least one of the nitrogens of the amine capping unitforming a zwitterionic alkoxylated polyol.